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Controlled release fertilizers

Article  in  Polish Journal of Chemical Technology · December 2007

DOI: 10.2478/v10026-007-0096-6

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 Polish Journal of Chemical Technology, 9, 4, 81 — 84, Pol.
2007,
J. Chem.
10.2478/v10026-007-0096-6
Tech., Vol. 9, No. 4, 2007 81

Controlled release fertilizers

Krzysztof Lubkowski, Barbara Grzmil
Szczecin University of Technology, Institute of Chemical and Environment Engineering, 70-322 Szczecin,
ul. Pu³askiego 10, Poland, e-mail: klubkowski@ps.pl

The efficiency of nitrogen assimilation by plants is rather low and this is a serious problem in view of
environmental protection. Improvement of nitrogen absorption can be carried out through the developing,
producing and applying the controlled release fertilizers. Biodegradable chitosan has been proposed as an
alternative material in the production of controlled release fertilizers.

Keywords: controlled release fertilizers, chitosan.

Presented at VII Conference Wasteless Technologies and Waste Management in Chemical Industry and Agriculture,
Miêdzyzdroje, 12 – 15 June, 2007.

INTRODUCTION pointed out that excessive amounts of fertilizers change the

degree of salinity and pH of the soil, leading to its gradual
Mineral fertilizers are some of the most important prod-
degradation5. Urea and ammonium salt, used as mineral
ucts of agricultural industry. While providing nutrients to
fertilizers, are potential sources of ammonia, which while
crops, they increase their growth and at the same time play
migrating into adjacent ecosystems disturbs or destroys the
an important role in regulating both the pH and the fertility
vegetation of other plants3. A part of ammonia, after conver-
of the soil. Production of mineral fertilizers has risen along
sion into nitric acid, combines with sulphuric acid and in the
with the increase of human population and the need for
form of acid rains badly affects vegetation and leads to ero-
increased food production1. However, an increased produc-
sion and soil depletion. As a result of the denitrification
tion of fertilizers and soil fertilization contrast with a rela-
process taking place in the soil, both nitrous oxide and nitric
tively low nutrient assimilation by crops; it is estimated that
oxide are created. They are responsible for the depletion of
for nitrogen the assimilation reaches 30 – 50%2, 3. The ef-
the ozone layer, subjecting people to the exposure of ultra-
ficiency of nitrogen assimilation depends on complex inter-
violet radiation. The production of mineral fertilizers is in
actions in crops' root systems, soil microorganisms, chemical
itself a risky factor, during which hazardous substances are
reactions taking place in the soil and the processes leading
released into the environment. These substances include sulfur
to adverse elimination of nitrogen from the soil. Most ferti-
oxides, nitric oxides, fluorine compounds and dust.
lizers are easily soluble in water, thus during their applica-
Little assimilability of mineral components also has
tion in water a soil solution with a given mineral compounds
unfavorable effects in the economic aspect of the issue; ni-
concentration is created. Nitrogen is absorbed from the soil
trogen losses, spent energy and human work effort negatively
by crops' root systems as NH4+ and NO3- mainly through
affect the total economic balance of the whole agrochemical
mass transfer. In order to make nitrogen assimilation more
production process. At the same time, a consumption of
effective, the fertilizer should be delivered no farther than 3
non-renewable sources of energy (such as natural gas) used
– 4 cm from the root system of a plant. If the amount of the
for the production of mineral fertilizers, should also be
delivered nitrogen exceeds the plant's intake capability, the
pointed out.
processes leading to a decrease of its concentration are ac-
All the above mentioned factors seem to violate the basic
tivated. These processes include both the physical processes
rule of natural environment protection, which aims at reach-
(rinsing out, vaporization) and microbiological conversions
ing a sustainable development ensuring fulfilling the needs
(replacement, precipitation, hydrolysis). It is worth noting
of present and future generations.
that an excessive concentration of mineral constituents and
In the light of the above presented facts, it seems that the
too high osmotic pressure of soil solution lead to a decrease
task of paramount importance is to increase the effectiveness
of water content, withering and an abnormal crop growth.
of plants' nitrogen absorption and to decrease nitrogen losses,
Low effectiveness of nitrogen assimilation causes serious
while at the same time to limit the amount of fertilizers'
problems in view of environmental protection. Because of
waste material produced by the industry. This can be carried
soil microorganisms mineral nitrogen undergoes transfor-
out through:
mation to nitrates easily soluble in the soil, which are later
– developing new technologies and methods of producing
leached from the soil to ground and surface waters. An
fertilizers (with a limited gas, dust and other waste material
increased concentration of nitrates in waters can be con-
emissions)
nected with the methemoglobina related diseases found in
– producing fluid – suspension fertilizers as well as those
children and in ruminant animals3 as well as with other
applied on plants' leaves (which eliminates the stages of
diseases (goitre, birth defects, heart diseases)1. The concen-
drying and granulation)
tration of nitrides and nitrosamines, i.e. the derivatives of
– developing, producing and applying fertilizers with a
nitrides present in water, was also associated with the diges-
delayed and controlled release of mineral nutrients (mainly
tive system diseases4. Nitrides also lead to an increased
nitrogen), i.e. the so-called controlled release fertilizers (CRFs).
eutrophication of surface waters5. An increased level of ni-
trates and nitrites in crops, which are the staple food for
people and animals, can negatively affect their health1. It was - 10.2478/v10026-007-0096-6
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82 Pol. J. Chem. Tech., Vol. 9, No. 4, 2007

NUTRIENT CONTROL RELEASE FERTILIZERS SCU – sulfur-coated urea is an example of this kind of a
6 fertilizer10, 11. Other examples include polysulfone-coated
According to specialists in fertilizers industry , fertilizers
urea12, polyethylene-coated urea13, and polymer-coated su-
market in the world (including even the stable European
perphosphate14. Other kinds of materials have also been
market) is going to undergo significant changes in order to
used for the coating of fertilizers and these include15: natural
reduce costs and maximize profits. The development and
gum, rosin, waxes, paraffins, various kinds of ester copoly-
application of the CRFs is going to be a basis of these
mers, urethane composites, epoxy and alkide resins,
processes.
polyolefines, polyacrylic acid, polyvinyl alcohol, epoxidized
Mineral constituent uptake (N, P, K) by plants in their
soybean oil with a polyester as a curing agent or butadiene-
vegetation cycle has a sigmoidal character1. An application
methylstyrene block copolymers.
of the CRFs which release their nutrients in a way better
The second kind of fertilizers is a system where the active
fitting plants' requirements ensures an improved effective-
component is dispergated in a polymer matrix. Two proc-
ness of fertilizing through minimizing the losses between
esses affect the rate of nutrients' release: diffusion in pores
application and absorption. At the same time using the CRFs
and canals of a matrix and physical and biochemical degra-
allows to reduce the negative influence fertilizers have on the
dation of a matrix. The system's great advantage is its simple
environment, largely due to high solubility of nitrogen com-
construction. The first study into a matrix system was pub-
pounds, which are left unused. In conventional fertilizing
lished in 198716, but up till now the system has not been
(e.g. with urea) nutrients release lasts 30 – 60 days, which
thoroughly studied17, nor has it been used in industrial ap-
given a 100 – 120 day long crops growth cycle means that
plications.
a fertilizers must be applied 2 or 3 times. The CRFs release
A distinct category of the CRFs are systems in which there
their nutrients slowly and gradually during the whole vegeta-
is no physical barrier in the form of a polymer material, and
tion season and consequently need to be applied once only,
in which the release rate decisive factor is either solubility
which greatly reduces both time and energy consumption. A
or degradability of a given fertilizer. Such fertilizers include1:
better and more efficient use of nutrients can lead both to a
– inorganic materials of low solubility (e.g. ammonium
reduction of waste material produced by the fertilizers indus-
and metallic phosphates)
try and to a reduction in natural gas consumption. It is also
– chemically or biologically degradable materials of low
pointed out that using the CRFs increases the crops' yield1, 7.
solubility (e.g. urea – formaldehyde condensates, oxamides,
The CRFs are the fertilizers which gradually release their
diurea.
mineral nutrients, while at the same time providing proper
The basis of selecting an appropriate fertilizer both the
nutrition to plants. They were first used in 19658. Currently,
mechanism and the rate of nutrients' release are assessed.
the CRFs are produced mainly in the USA, Western Europe,
From the technological point of view the CRFs can be di-
Japan, South Korea, Israel and China.
vided into these in which the release is controlled by coating
Most studies quoted in the literature on the subject men-
diffusion, coating erosion, chemical reaction, osmosis or
tion a system in which a granule of fertilizer is encapsulated,
swelling1. The kinetics of nutrients' release is a process, which
i.e. it is coated with an inert layer. After a fertilizer's appli-
so far has not been entirely understood. Although the litera-
cation, water penetrates through a hydrophobic membrane
ture on the subject presents several kinetic equations describ-
into the inside of a granule. Then, nutrients are dissolved and
ing the release rate, these equations mainly refer to the coat-
the arising osmotic pressure leads to either a partial tearing
ing diffusion cases18.
off of the membrane or to its expansion, which allows ion
However, none of the earlier presented modern technolo-
transport through the coating into the soil9 (Figure 1). The
gies assures a proper and full balance between a plant's
rate of nutrients' release is controlled by a coating diffusion
changing biological needs for nitrogen and its release. Fer-
coefficient.

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Figure 1. Stages of the release from a polymer-coated granule Downloaded from PubFactory at 07/26/2016 05:55:14PM
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tilizers coated with sulfur have a high initial release rate (as
a result of badly damaged coating), whereas for the polymer
coated fertilizers nitrogen release rate is at first low and it
gradually increases along with the increase of water penetrat-
ing the inside of a granule. As for formaldehyde - urea resins
coatings, they release nitrogen at a slow and constant rate. To
sum up, it would seem reasonable to look for complemen-
tary materials that would combine a high rate and the stabil-
ity of nutrients' release, while at the same time fulfilling
crops' nutritious needs.
Despite the CRFs's many advantages and the fact that they
have been constantly developed, their use is still very limited.
It is estimated that the CRFs constitute a mere 1 per cent of
the total amount of used fertilizers. This is due to the CRFs's
high prices; they are from 2 to 8 times more expensive than
the commonly used fertilizers1.
Making good use of the enormous potential connected
with the CRFs's market, which in fact means developing,
producing and applying the CRFs requires solving how to:
– produce fertilizers at a cost lower than the presently
manufactured CRFs
– control the features of the currently developed fertilizers
– understand the mechanism of the controlled release
better
– develop the kinetic models of the controlled release for
new systems
– develop new research methods of the controlled release
– carry out the initial assessment of a selected CRF group
on the environment
THE POSSIBILITY OF USING CHITOSAN IN CRFS
One of the CRFs' drawbacks, and particularly the poly-
mer-coated CRFs, is that after nutrients' consumption there
is still a considerable amount of useless polymer left in the
soil. A good and possible solution, although not as yet used
on a technological scale, is to produce the CRFs using bio-
degradable materials17, manufactured from raw materials
renewable in the process of biosynthesis. Chitosan is one of
such materials. It is a natural polysaccharide produced com-
mercially by deacetylation of chitin, which is the structural
element in see crustaceans. Chitosan easily undergoes bio-
degradation in natural environment and it is highly
biocompatible. Additionally, it has unique polycationic prop-
erties. Owing to its features it is being intensively investi-
gated in the pharmaceutical field, as it might be used in the
systems of controlled drugs release19 – 21. For several years
now, researchers have been investigating the possibility of
using chitosan in agrochemical industry. A review of the
literature on the subject seems to suggest that the main area
of research is focused on how to use chitosan as a nutrient
in organic or mineral fertilizers, which can improve soil's
fertility, enhance plants' growth and stimulate crops' yield.
Between 2000 and 2006, 51 patents were obtained (in China,
South Korea and Japan) and 8 articles were published on the
subject (5 of them in English)22 – 26. The interest of using
chitosan as a fertilizer's compound, which could be respon-
sible for nutrients' controlled release, is relatively small.
Between 2000 and 2006 nine patents were registered27 – 35
and six articles were published (none of which was published
in English) on the subject of using CRFs with chitosan.
Nevertheless, in the literature available on the subject there
is no data on this kind of fertilizers' functionality, rate and
Pol. J. Chem. Tech., Vol. 9, No. 4, 2007 83
the effectiveness of nutrients' release, utilitarian properties,
or their influence on the environment.
ACKNOWLEDGEMENT
This work is supported by Grant No. N205 038 32/2216.
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